Proteinized hosiery



Patented Mar. 12, 1940 UNITED STATES I PATENT OFFICE PROTEINIZED H SIERY No Drawing. Application December 23, 1937, Serial No. 181,294

11 Claims.

The present invention relates to hosiery and in particular to improved proteinized hosiery and the method of making the same. More specifically, the present invention is directed to the replacement of a protein protective agent upon fibers in which the original protective agent has been substantially removed in processing.

Silk, wool and other fibers possess inherent'undesirable characteristics with which the hosiery l0 industry have been struggling for years to overcome. For example, natural silk has the firmness, strength and body desired, but through processing a relatively high percentage of the protective protein gum supplied by nature is re- 15 moved and the silk becomes hygroscopic, pervious to dirt, perspiration and the like, which makes the fiber susceptible to rapid deterioration. Returning a protective agent to fibers, which restores strength, firmness and bodywithout diminishing in any way the desirable qualities obtained through processing has long been a problem of the manufacturers of hosiery.

Many treatments have been attempted in the past but all have failed to fully accomplish the s essential requirements. Some of the better known treatments have been, dipping the hosiery in solutions of mineral salts, such as barium chloride with subsequent treatment with a sulphate to produce barium sulphate, sizing with starch, glues and waxes, sizing with mineral soaps such as aluminum oleate, etc. All of-these prior treatments have had objectionable features, such as, the inability to apply evenly and uniformly, the changing of the appearance from that of natural silk to an artificial silk, lack of permanencythe fact that they were easily washed out, their tendency to stiffen and harshen the fabric, the danger of rancidity after the goods had been stored for a certain length of time, stickiness or adherence to the heated shaping forms, their relatively high cost, etc. The art has long recognized the inadequacies of the known treatments and the need of new processes and compositions adapted to improve hosiery free from the above 46 noted objections.

Therefore, the principal object of our invention is to provide processes and compositions adapted for use in the manufacture of improved hosiery free from disadvantages "enumerated 50 above.

Further objects will be apparent as the description hereinafter proceeds.

We have discovered that the stable protei emulsions such as described in our prior patents F and applications and particularly our co-pending application, Serial No. 76,008, are adapted for use in the manufacture of improved hosiery. The hosiery treated with our novel emulsion comprising finely divided waxy material dispersed in an aqueous medium containing a relatively high per-' a centage of protein material and a smaller amount of a water soluble emulsifying agent, are free from the disadvantages encountered in treating hosiery with the prior compositions and particularly the prior wax containing compositions. For 10 example, hosiery treated with our emulsion as hereinafter described are not stiii or harsh nor do they take on a luster or sheen making silk hose resemble imitation silk such as rayon. Our emulsion when precipitated on the fibers of the 16 hose is not readily washed out and tests have shown the treated hose to have greatly increased wearing qualities. No difficulty is encountered in uniform application of our emulsion to the hose, the hose being free from both wax and pro- 20 tein spots. In addition, hose treated with our emulsion do not stick to the shaping forms which may in part be accounted for by the presence of a protective film of insolubilized protein sur-' rounding the minute particles of wax. 25

In our present process we have overcome all of the objectionable features of the prior processes and have secured all of the desirable features. Our treatment rather than detracting from the appearance of the fibers, actually en- 30 hances the colorings. In addition, by our process we restore the same type of protecting agent,

i. e. protein, that was removed through processing. In fact, for practical purposes we have improved on nature herself by putting the protein 35 back in a form in which it is insoluble in water.

.- the same to agitation, do notagglomerate 'on heating, neither do they agglomerate due to the hydrolytic action of water, nor do they agglomerate in the presence of lime salts in hard water. In practice we have found it desirable to break or precipitate the emulsion by addition of a small amount of dilute acidic material. While we do not wish to limit ourselves to any particular theory of action, our investigations indicate that the 5 emulsion when broken by acidic material forms minute particles of wax coated with a film of insolubiliz'ed protein which prevents coalescence of the wax and proteininto large particles. In other words, the protein and waxy material which lat- About 30 pounds of soya bean casein is added to about 13 gallons of water heated to a temperature of about 140-150 F. and the mixture stirred for about 5 minutes until the protein swells. About 1.5 pounds of caustic soda (5 percent based on the weight of the casein) dissolved in about 1 gallon of water is added to the water-casein mixture which is maintained at a temperature of about 140-150 F. and stirred for about 15 minutes or until the protein is completely dispersed or dissolved. To the alkaline casein solution is next added about 15 pounds of ammonium oleate. About pounds of a molten waxy material such, for example, as melted parafiin wax (m. pt. 124 F.) is then added to the dispersion. The mixture is next preferably subjected to a suitable high speed agitator capable of attaining about 600 to 1700 R. P. M. for about 30 minutes to insure uniform dispersion. Complete dispersion is attained when the melted parafiin or oil no longer remains on the surface of the emulsion. Warm water may be added to the protein-wax emulsion so as to obtain the desired flow characteristics or viscosity.

In a separate container about 60 pounds of soya casein is mixed with about 125 gallons of water at a temperature of about F. To this mixture is next added about 3 pounds of caustic soda dissolved in a small amount of water. The mixture is then stirred for about 15 minutes until the protein is completely dispersed. The original protein-wax emulsion, the preparation of which is described above, is then added to the protein dispersion with proper stirring and the final emulsion diluted with warm water to the desired consistency.

The complete emulsion described in the above example contains a 1:1 protein to wax ratio and is ordinarily preferred in the treatment of silk hosiery. In practice, it has been found desirable to add a small amount of a suitable preservative to the complete emulsion such, for example, as

1.0 percent formaldehyde based on the weight of the dry protein.

It will be understood that the above example is not to be interpreted as limiting our invention. For example, the soya bean casein for which may be substituted any water insoluble, acid precipitable protein such as milk casein, may be added in a single addition instead of forming the separate dispersions as above described. In place of the caustic' soda employed in the above example, any alkaline protein solubilizing composition may be used including ammonium and alkali hydroxides and alkaline reacting salts such as borax, the sodium carbonates and. the tri anddisodium phosphates. If an. alkaline reacting salt is used in place of the strongly alkaline sodium hydroxide employed above, it has been found necessary to use a slightly higher proportion of solubilizing salt. For example, if sodium carbonate (soda ash) is used about 7 percent based on the weight of the protein hasbeen found sufficient to give complete and uniform dispersion. In place of the ammonium oleate used in the above example, any suitable emulsifier may be employed such as the sulphonated oils, Turkey red oil, soluble soaps of any nature, triethanolamiiie, gums such as gum arabic, etc. Our investigations have shown that the proportion of emulsifying agent used should be atleast about one-eighth of the amount of waxy wax, natural waxes, inert fats and oils and the I like.

It will likewise be understood that our invention is not limited to the above temperatures and proportions of the various ingredients used in our preferred process. For example, our investigations have shown that a 1:4 to 4:1 protein to wax ratio may be employed. The use of less protein than that required in a 1:4 protein to wax ratio increases danger of wax agglomeration and formation of wax spots when the emulsion is broken and is, therefore, not practical for commercial application. The use of more protein, which is a relatively expensive material, than that required in a 4:1 protein to wax ratio has not been found to be of proportional advantage. In addition, in an emulsion containing over a 4:1

protein to wax ratio the danger of protein agglomeration when the emulsion is broken upon addition of acidic material is increased. In practice, the use of a 1:2 or 2:1 protein to wax ratio is often desirable, although for silk hosiery a ratio of about 1:1 protein to wax is preferred. In place of the preferred high speed stirrer above indicated, any suitable type colloidal mill or homogenizing equipment may be substituted therefor.

The emulsion, prepared for example as above described, may be applied in any suitable manner to the fibers either prior or subsequent to knitting. In practice, we have found it desirable to apply the emulsion to the knitted hose just after the completion of the dyeing operation when the fibers are still moist. In our preferred process the moist stockings or socks are placed in a suitable container such as a rotary dye"machine and are soaked in the emulsion contained therein for about 15 minutes. The hose are then placed in an extractor centrifuge for about 1 minutes to remove excess emulsion. The hose are next placed in another vat or container and treated for about 13 minutes with a dilute acidic.

solution such as a one-eighth percent iron free paper makers alum solution. The hose are then placed in an extractor centrifuge to remove excess alum solution. If desired, the protein may be hardened by additional treatment with formaldehyde'or other well known protein insolubilizing agents. Throughout the treatment the emulsion bath may be adjusted to the desired concentration by addition of water or by addition of fresh emulsion. In practice, we have found a concentration of about 1.8 percent to be preferred when treating silk hosiery, although concentrations of about 0.5 to 2.5 percent give satis factory results. The optimum. concentrations which depend upon the type of hosiery to be treated may be ascertained by simple experimental tests.

It will be understood that our invention is not limited to the above described method of emulsion application. Any suitable manner of incorporating the emulsion into the hosiery so as to. thoroughly impregnate the threads or fibers may be employed. The times given in the above example are only illustrative and may be varied as desired to suit the weight of the hosiery treated, etc. It will also be understood by those skilled in the artthat our. invention is not limited to the use of the above described acidic agent. Any acidic agent or acid reacting salt, such as aluminum sulphate, that will break the alkaline protein-wax emulsion, may be used. The acidic reagents employed should be such as do not deleteriously affect the colors of the dyed fibers.

Our invention is adaptable for all types of hosiery including silk, wool, and cotton hose as well as hosiery made from synthetic compositions such as rayon. However, as pointed out above, our invention is particularly adaptable for use in the manufacture of improved silk hose. Silk treated in accordance with our process in which protein is precipitated upon the fibers is rendered non-hygroscopic and impervious to dirt. For similar reasons, our invention involving the replacement of protein is also particularly adaptable for use with wool hosiery as the processing of wool fibers is accompanied by the loss of wool albumen. Our invention is also particularly adaptable for use with cotton fibers which have undergone a mercerized treatment.

The hosiery treated with our emulsion has increased strength and prolonged tests show the treated hosiery to have greatly increased resistance to wear. hosiery treated in accordance with our invention resides in the binding effect of the precipitated protein upon the fibers and: strands which reduces snagging and runs". Another great advantage and of particular importance to wearers of silk hosiery resides in the fact that our improved hosiery is splash-proof. A still further advantage found in our improved hosiery is that the treated hosiery is resistant to body acids and like compositions which cause fiber disintegration.

Our improved hosiery not only has increased wear but the treated hosiery also holds its shape much better than untreated hosiery. The treated hosiery is firm and yet flexible and has a soft feel. The proteinizingof hosiery in accordance with our invention puts a bloom into the color of the hose and adds greatly to the depth of color both of which are highly desirable.

One of the greatest advantages of our invention was in the discovery that our emulsion tempers' the hose threads and makes them flexible. The flexibility of the individual threads makes better stitching possible, i. e. stitching of uniform structure. For example, the proteinizing of the hosiery threads either prior or subsequent to knitting reduces coarseness and unevenness in the stitch pattern.

In addition to the above, our hosiery, which is water-proof, is easily washed. The proteinizing of the hosiery keepsthe dirt on the surface of the hose from where it can be readily removed without danger of injury to the thread structure.

The present invention is a continuation in part of our co-pendingapplication, Serial No. 76,008, filed April 23, 1936, for Emulsions.- Attention is also directed to our copending application, Serial No. 71,184, filed March 27, 1936, and .our prior Patents Nos. 2,058,085, 2,059,464 and 2,059,465, which relate to the paper industry and in particular to the incorporation of wax into paper. The present invention, on the other hand One great advantage foundin as described above, is directed in particular to the incorporation of protein into hosiery.

Although we have illustrated our invention with a preferred process and specified ingredients,

it will be understood that our invention is not 5 limited thereto. For example, our emulsion may be applied without subsequent treatment with acidic material, although the precipitation with alum or the like is preferred. Likewise, although we prefer to apply the emulsion to the hose and .then treat with an acidic solution the reverse,

i. e. initial treatment with alum and subsequent application of the emulsion, may be followed, if desired. All modifications coming within the spirit and scope of our invention are intended to be covered by the following claims.

We claim: 7

1. The step in the method of treating hosiery which comprises applying to hosiery an emulsion consisting of an aqueous alkaline dispersion containing a water insoluble, acid precipitable protein, particles of waxy material and an emulsifying agent, the ratio of protein to waxy material being 1:4 to 4:1 so that the protein surrounds and forms a film about the particles of waxy material preventing agglomeration of both the protein and waxy material when the emulsion is broken by addition of acidic material.

2. The steps in the method of treating hosiery which comprises impregnating hosiery with an emulsion consisting of an aqueous alkaline dispersion of a water insoluble, acid precipitable protein, particles of waxy material and an emulsiiying agent, and breaking the emulsion contained in the hosiery'by treating the same with a dilute acidic material, the ratio of protein to waxy material being 1:4 to 4:1 so that the protein surrounds and forms a film about the particles of waxy material preventing agglomeration of both the protein and Waxy material when the emulsion is broken upon addition of the acid material.

3. The steps in the method of treating hosiery which comprises impregnating hosiery with an emulsion consisting'of an aqueous alkaline dispersion of casein, inert waxy material' and a soap emulsifying agent, and breaking the emu1-' sion contained in the hosiery by treating the hosiery with acidic material, the ratio of casein towaxy material being about at least 1:2 to 2:1.

4. The steps in the method of treating hosiery which comprises impregnating silk hosiery with 'an emulsion consisting of an aqueous alkaline dispersion of soya bean casein, mineral wax, and an emulsifying agent, removing excess emulsion from the hosiery and breaking the emulsion remaining in the hosiery by impregnating the hosiery with a dilute acidic solution containing iron free paper makers, alum, the ratio of'casein.

to wax being about :1.

5. The steps in the method of treating hosiery which comprises impregnating silk hosiery with an emulsion consisting of an aqueous alkaline dispersion of soya bean casein, parafin, and ammonium oleate, removing excess emulsion from the hosiery and breaking the emulsion remaining in the hosiery by impregnating the hosiery with a dilute acidic solution containingironfree paper makers alum, the ratio of casein to parafiln being about 1:1.

6. The method of precipitating protein mate- 70 A rial upon fibers particularly adapted for use in the manufacture'of hosiery, which comprises treating the fibers with an emulsion consisting of an aqueous alkaline dispersion of casein, inert waxy material and an emulsifying agent and breaking the emulsion retained by the fibers by treating the fibers with a dilute solution of paper makers alum, the ratio of casein to waxy material being about 1:1 and the ratio of emulsityingagent to waxy material being about 1:6.

"7. As a new article of manufacture, hosiery having incorporated therewith a composition siery having incorporated therewith a composition consisting of minute particles of paraflln surrounded by a film of insolubilized soya casein, the ratio of casein to paraflin being about 1:1.

10. A silk stocking having the threads thereof impregnated with a composition consisting 01" minute particles of a lubricating inert waxy material coated with an acid precipitated waterinsoluble protein, the ratio of protein to waxy material being about 1:2 to 2:1.

11. A silk stocking having precipitated on the fibers thereof, the aluminum sulfate precipitate of an aqueous emulsion consisting of an alkaline dispersion of soya beanprotein, a soap emulsifying agent and mineral wax, the ratio of pro- 14 tein to wax being about 1:1.

O'I'IO KRESS. CHARLES E. JOHNSON. 

